[0001] The present invention relates, in a general manner, to polymerizate-based polymer
blends comprising groups of tetrafluoroethylene derivatives (designated hereinbelow
by tetrafluoroethylene polymerizate) and to their process for manufacture, to the
articles obtained by extrusion moulding, extrusion blow moulding and injection moulding
of these blends, as well as to the use of these blends in polymer compositions.
[0002] More particularly, the present invention relates to a polymer blend including tetrafluoroethylene
polymerizate particles totally or partially encapsulated by a polymer or copolymer
resulting from the polymerization of monomers or mixtures of monomers which can be
emulsion-polymerized, in particular by radical route, the said polymer blend being
substantially free of tetrafluoroethylene polymerizate filaments forming a network
connecting the particles.
[0003] The polymer blend may be obtained in the form of a free-flowing powder which does
not have a tendency to block, thereby making it particularly easy to handle and store,
in particular in any type of plastic for which the handling of a polymerizate including
groups of tetrafluoroethylene derivatives proves difficult.
[0004] The polymer blend, when it is incorporated in an effective quantity into a polymer
composition, in particular a fire-retarded polymer composition, surprisingly improves
the fire resistance without impairing the mechanical properties of the polymer composition,
and surprisingly even improves some of the mechanical properties of the composition,
such as, for example, the tensile elongation and the impact strength.
[0005] Document DE-A-3,903,547 describes mixtures of polysiloxane-polycarbonate block copolymers
and PTFE which are used as rigid thermoplastics, having a good environmental stress
cracking resistance. The mixture may be obtained, inter alia, by synthesizing the
block copolymers in the presence of the required quantity of PTFE.
[0006] Document EP-A-0,166,187 describes a powder composition containing a tetrafluoroethylene
polymerizate. The powder is obtained by mixing a dispersion of poly(tetrafluoroethylene)
with a latex of grafted polymerizate, for example an acrylonitrile-butadiene-styrene
grafted polymerizate, filtering and drying in order to obtain a powder.
[0007] The powders obtained in this way by coprecipitation (or alternatively called co-coagulation
or co-flocculation powders) have the drawback of having high self-adhesion, in particular
for high PTFE contents, for example 25% by weight or more, and as a result do not
flow freely, thereby making them difficult to handle and to store.
[0008] The subject of the invention is a polymer blend according to claim 1 which includes
tetrafluoroethylene polymerizate particles, totally or partially encapsulated by a
polymer or copolymer, and which is substantially free of tetrafluoroethylene polymerizate
filaments forming a network connecting the particles of the blend together, and being
in the form of a free-flowing powder.
[0009] The subject of the present invention is also a process for preparing a polymer blend
according to claim 1 which includes tetrafluoroethylene polymerizate particles totally
or partially encapsulated by a polymer or copolymer and being in the form of a free-flowing
powder, the polymer blend being substantially free of tetrafluoroethylene polymerizate
filaments forming a network connecting the particles of the blend together.
[0010] A further subject of the invention is articles obtained, for example, by extrusion
moulding, extrusion blow moulding and injection moulding of the polymer blend.
[0011] Finally, the subject of the invention is compositions, in particular fire-retarded
compositions, comprising the novel polymer blend, the compositions obtained having
improved fire-resistance properties and mechanical properties.
[0012] According to the invention, a polymer blend is produced which includes tetrafluoroethylene
polymerizate particles totally or partially encapsulated by a specified polymer or
copolymer obtainable by polymerization of monomers or mixtures of monomers which can
be emulsion-polymerized, in particular by radical route.
[0013] The tetrafluoroethylene-polymerizate-based blend is essentially characterized by
a morphology different from that of tetrafluoroethylene-polymerizate-based polymer
blends obtained by coprecipitation and in that it is virtually free of tetrafluoroethylene
polymerizate filaments forming a network connecting the particles of the blend together,
in particular for relatively high tetrafluoroethylene polymerizate contents.
[0014] As tetrafluoroethylene polymerizate, it is possible to use, in the polymer blends
of the present invention, poly(tetrafluoroethylene), tetrafluoro-ethylene-hexafluoroethylene
copolymers, and copolymers of tetrafluoroethylene with small quantities of copolymerizable
ethylenically unsaturated monomers. These polymers are known and are described, inter
alia, in "Vinyl and related polymers", Schildknecht, John Wiley & Sons, Inc., New
York, 1952, pages 484-494, and "Fluoropolymers" Woll, Wiley-Interscience, John Wiley
& Sons, Inc., New York, 1972.
[0015] Preferably, poly(tetrafluoroethylene) is used.
[0016] The polymers and copolymers for encapsulating the tetrafluoroethylene polymerizate
may be any polymer or copolymer obtained from monomers or mixtures of monomers which
can be emulsion-polymerized, in particular by radical route.
[0017] According to the present invention, the polymers are polystyrene and poly(α-alkylstyrenes),
in particular poly(α-methylstyrene).
[0018] The copolymers for the blend of the present invention are styrene-acrylonitrile (SAN)
and acrylonitrile-butadiene-styrene (ABS) copolymers, α-alkyl-styrene-acrylonitrile
copolymers, in particular α-methylstyrene-acrylonitrile (AMSAN) copolymers, styrene-butadiene
rubbers (SBR), and their mixtures.
[0019] Most particularly recommended as copolymers are styrene-acrylonitrile and α-methylstyrene-acrylonitrile
copolymers.
[0020] The proportion of tetrafluoroethylene polymerizate in the polymer blend of the invention
may vary widely and is generally between 0.01 and 80% by weight with respect to the
total weight of polymers in the blend, and preferably between 0.05 and 70% by weight.
[0021] The polymer blend according to the invention may be prepared simply by emulsion polymerization,
preferably by radical route, of a monomer or a mixture of monomers in the presence
of a polytetrafluoroethylene latex. Various emulsion-polymerization processes may
be used to produce the encapsulation polymer, for example a discontinuous, semi-continuous
or continuous emulsion. The term emulsion used in the present application denotes
an emulsion alone or an emulsion-suspension.
[0022] The polymerizate latex including groups of TFE derivatives may be introduced into
the reaction medium for polymerizing the encapsulation polymer or copolymer right
from the start, that is to say before any polymerization has begun, or during the
polymerization, generally before 90% by weight or more of the monomers have been polymerized
or copolymerized.
[0023] Generally, the tetrafluoroethylene polymerizate latex comprises 20 to 80% by weight
of solids, and the particle size of this latex is between 0.05 and 20 µm (measured
by laser diffraction), preferably between 0.1 and 1 µm.
[0024] Emulsion polymerization by radical route is a well known process. The radical polymerization
is described, inter alia, in the work "Chemie macromoléculaire [Macromolecular chemistry]",
volume 1, chapter III, by G. CHAMPETIER, HERMANN.
[0025] Once the polymerization of the encapsulation polymer has been accomplished, the next
step is coagulation and drying, in order to obtain a powder of polymer blend which
flows freely, does not have a tendency to block and is substantially free of tetrafluoroethylene
polymerizate filaments forming a network connecting the particles of the blend together.
Examples 1 to 3
[0026] Polymer blends according to the invention, including tetrafluoroethylene polymerizate
particles encapsulated by a styrene-acrylonitrile (SAN) copolymer were prepared using
a semi-continuous emulsion process.
Polymerization:
[0027] The blends, comprising PTFE particles encapsulated by the styrene-acrylonitrile copolymers
(PTFE/SAN) were prepared in the following manner:
a 15 litre reactor was used at a temperature of 60°C and stirred at 120 revolutions
per minute. The SAN copolymer was prepared by using a ferrous-ion/cumene hydroperoxide
(CHP) redox system as a radical initiator in combination with an ethylenediaminetetraacetic
acid (EDTA) chelating agent and sodium hydroxymethanesulphinate dihydrate (SFS) as
reducing agent. t-Dodecyl mercaptan (TDM) was used as chain-transfer agent. The tetrafluoroethylene
polymerizate latex was introduced in the form of a solution of the polymerizate in
a soap. The soap system was tallow fatty acid (TFA). The reactor was initially charged
with the entire soap/tetrafluoroethylene-polymerizate solution and with 15% by weight
of all the other solutions (SFS/EDTA solution, FeSO
4 solution and monomer/TDM solution), before starting the feed with initiator. Next,
only the CHP initiator was introduced for a certain time before starting the feed
of all the other solutions. Once the feeds were completed, the reactor was kept stirred
at a temperature of 60°C during a maximum post-polymerization step of 180 minutes.
A blend of tetrafluoroethylene-polymerizate/SAN was obtained in this way.
[0028] The details of the manufacturing processes and of the blends obtained are indicated
in Table 1 below.
TABLE 1
EXAMPLE No. |
1 |
2 |
3 |
SAN/PTFE ratio |
50/50 |
50/50 |
40/60 |
Solids content (theoretical) |
24.3% |
34.6% |
34.6% |
|
Initial charge of the reactor: |
Soap/PTFE solution: |
parts by weight |
parts by weight |
parts by weight |
Water |
106 |
114 |
114 |
PTFE (dry) |
25 |
50 |
60 |
Water of the PTFE |
14.676 |
28.964 |
34.757 |
TFA (tallow fatty acid |
0.285 |
0.570 |
0.456 |
KOH |
0.0685 |
0.1507 |
0.1206 |
|
Reactor heated to 60°C then addition of: |
Solution of monomers: |
|
|
|
Styrene |
2.5926 |
5.2830 |
4.2264 |
Acrylonitrile |
1.1111 |
2.2642 |
1.8113 |
TDM |
0.0148 |
0.0302 |
0.0242 |
SFS/EDTA solution: |
|
|
|
Water |
4.2963 |
5.2075 |
4.3774 |
SFS |
0.0100 |
0.0204 |
0.0163 |
BDTA |
0.000207 |
0.0004 |
0.0003 |
FeSO4 solution: |
|
|
|
Water |
0.7778 |
1.5094 |
1.5094 |
FeSO4, 7H2O |
0.000081 |
0.0002 |
0.0001 |
|
t = 0, start of feed: |
CHP |
0.4 |
0.2 |
0.16 |
Feed time (min) |
27 |
53 |
53 |
|
Start of feed of: |
Solution of monomers: |
|
|
|
Styrene |
14.9074 |
29.7170 |
23.7736 |
Acrylonitrile |
6.3889 |
12.7358 |
10.1887 |
TDM |
0.0852 |
0.1698 |
0.1358 |
SFS/EDTA solution: |
|
|
|
Water |
24.7037 |
29.2925 |
24.6226 |
SFS |
0.0575 |
0.1146 |
0.0917 |
EDTA |
0.0012 |
0.0024 |
0.0019 |
FeSO4 solution: |
|
|
|
Water |
4.4722 |
8.4906 |
8.4906 |
FeSO4, 7H2O |
0.0005 |
0.0009 |
0.0007 |
Feed time (min) |
23 |
45 |
45 |
Reactor kept at 60°C after completing the feeds: |
Time (min) |
120 |
180 |
180 |
[0029] The conversion (based on the solids content) and the pH were monitored as a function
of time for each example.
[0030] The results are indicated in Table 2.
TABLE 2
|
Example 1 |
Example 2 |
Example 3 |
Time (min) |
Conversion (%) |
pH |
Conversion (%) |
pH |
Conversion (%) |
pH |
0 |
1.11 |
9.56 |
1.04 |
10.01 |
4.8 |
9.83 |
15 |
|
|
1.57 |
10.08 |
4.21 |
9.94 |
19 |
7.22 |
9.62 |
|
|
|
|
30 |
21.55 |
9.61 |
8.92 |
10.06 |
9.49 |
9.84 |
45 |
44.68 |
9.5 |
29.24 |
9.89 |
28.58 |
9.62 |
60 |
62.8 |
9.43 |
51.37 |
9.75 |
51.57 |
9.56 |
75 |
69.22 |
9.38 |
|
|
|
|
90 |
73.42 |
9.35 |
85.79 |
9.5 |
85.71 |
9.41 |
105 |
77.46 |
9.23 |
|
|
|
|
120 |
80.67 |
9.28 |
91.62 |
9.56 |
93.22 |
9.35 |
135 |
83.8 |
9.15 |
|
|
|
|
150 |
87.25 |
9.15 |
93.06 |
9.56 |
95.02 |
9.31 |
180 |
|
|
93.7 |
9.55 |
95.82 |
9.32 |
210 |
|
|
93.87 |
9.59 |
96.18 |
9.28 |
233 |
|
|
93.7 |
9.5 |
96.32 |
9.28 |
Coagulation and drying:
[0031] The polymer blends obtained were introduced in an acid solution (two parts of sulphuric
acid in water) and heated to 95°C with vigorous stirring. The solids content was 15%
by weight. Introduction of the blend latices was completed in approximately 10 minutes.
The slurry obtained was kept stirred at this temperature for 20 minutes before centrifuging.
The powder obtained was then re-impasted for 30 minutes at 55°. The solids content
of the paste was 18%. After centrifugation, the powder obtained was dried in a fluidized-bed
dryer at a temperature of 60°C for approximately 2 hours. A free-flowing powder having
a final moisture content of between 0.3 and 0.4% was obtained.
[0032] By way of comparison, a polymer blend of polytetrafluoroethylene and SAN was prepared
containing 50% by weight of PTFE and 50% by weight of SAN by coagulation (coprecipitation),
under identical conditions, from a mixture of SAN latex and PTFE latex.
[0033] The flowability of the powders obtained was evaluated using a funnel test. The results
are indicated in Tables 3 and 4 below.
TABLE 3
|
funnel diameter (mm) |
15 |
10 |
8 |
5 |
3.5 |
|
|
time (s) |
1.5 |
4 |
7 |
22 |
126 |
pure SAN |
number of taps on the funnel |
0 |
0 |
0 |
0 |
22 |
|
|
time (s) |
no flow |
|
|
|
|
|
PTFE/SAN 50/50 coprecipitation |
number of taps of the funnel |
|
|
|
|
|
|
PTFE/SAN 50/50 |
time (s) |
4 |
8 |
14 |
no flow |
|
|
Example 1 |
number of taps on the funnel |
0 |
0 |
2 |
|
|
|
PTFE/SAN 50/50 |
time (s) |
2.5 |
5.5 |
9 |
44 |
no flow |
|
Example 2 |
number of taps on the funnel |
0 |
0 |
0 |
3 |
|
|
PTFE/SAN 60/40 |
time (s) |
4.5 |
16 |
34 |
no flow |
|
|
Example 3 |
number of taps on the funnel |
0 |
2 |
8 |
|
|
TABLE 4
Particle size (µm) |
pure SAN |
PTFE/SAN 50/50 coprecipitation |
PTFE/SAN 50/50 Example 1 |
PTFE/SAN 50/50 Example 2 |
PTFE/SAN 60/40 Example 3 |
>1000 |
26.9% |
|
23.5% |
33.6x% |
9.9% |
> 800 |
36.9% |
not |
36.9% |
43.7% |
14.9% |
< 160 |
2.2% |
|
3.8% |
3.3% |
20.4% |
< 63 |
- |
measurable |
0.9% |
1.0% |
4.8% |
< 50 |
- |
|
0.7% |
0.9% |
- |
average |
695 |
|
650 |
720 |
360 |
[0034] The results show that the powders of blends according to the invention flow much
more easily than the powder obtained by coagulation. Particle-size measurements were
also carried out on each of the powders by passing them through a series of screens.
The particle size of the powder obtained by coagulation of a latex mixture could not
be measured because of the self-adhesion of the powder, preventing it from passing
through the screens. It will be noted that this self-adhesion phenomenon increases
with the PTFE content of the blend. It is clear that the powders of blend according
to the invention have a considerably lower tendency than the powders obtained by coagulation
of a latex mixture, in particular for high PTFE contents.
[0035] Photomicrographs of the powders of the blend according to the invention and of the
powder obtained by coprecipitation of a latex mixture were also obtained.
[0036] Figure 1 is a scanning electron micrograph (magnification 25000 ×) of the 50/50 PTFE/SAN
blend powder obtained by coprecipitation of a latex mixture. As this figure shows,
the SAN particles are linked by PTFE filaments.
[0037] Figures 2 and 3 are scanning electron micrographs (magnification 25000 ×) of the
blends of Examples 1 and 3, according to the present invention.
[0038] Although in Figure 1 the number of filaments connecting the powder particles are
so numerous that they prevent the powder from flowing freely, as may be seen in Figures
2 and 3, the powder has no filaments joining the particles in the case of the blend
of Example 1 and virtually no filaments in the case of the blend of Example 3, so
that the powders obtained flow freely, even with a level of PTFE as high as 60% by
weight.
[0039] As indicated previously, the blends according to the invention can be used directly
to obtain articles by extrusion moulding, extrusion blow moulding or injection moulding.
[0040] The blends according to the invention prove to be particularly useful for increasing
the fire resistance of polymer compositions, in particular fire-retarded polymer compositions.
[0041] The tetrafluoroethylene polymerizates have already been used as anti-drip agents
in fire-retarded polymer compositions. However, the use of these polymerizates has
several drawbacks. In particular, compositions containing such tetrafluoroethylene
polymerizates lead to extruded films having a very poor surface appearance, exhibiting
non-melted particles at the surface or the tetrafluoroethylene polymerizate forms
a fibrous network in the polymer matrix, which results in very low impact strength
characteristics. Finally, the incorporation of these tetrafluoroethylene polymerizate
powders tends to increase the opacity of the initially transparent matrices.
[0042] Apparently, these defects are due to poor dispersion of the tetrafluoroethylene polymerizate
particles in the matrix of the composition.
[0043] The incorporation of the tetrafluoroethylene-polymerizate-based blends according
to the invention remedy the above drawbacks.
[0044] In particular, the use of these encapsulated tetrafluoroethylene-polymerizate-based
blends makes it possible to obtain a high tetrafluoroethylene polymerizate content
in a masterbatch (for example greater than 40%), this being virtually impossible to
obtain using other ways of preparing the masterbatch (for example by co-coagulation
of polytetrafluoroethylene latex with a latex of the polymer support). The encapsulated
tetrafluoroethylene-polymerizate blends are easily dispersible and are compatible
with the matrix, the very fine particles of tetrafluoroethylene polymerizates being
uniformly dispersed, which results in excellent surface appearance of the injection-moulded
or extrusion-moulded parts while still keeping the other excellent properties of the
composition.
[0045] In particular, the use of the blends according to the invention does not adversely
affect the impact strength, in particular the multiaxial impact strength, and the
Izod impact strength, even with high levels of tetrafluoroethylene polymerizate (for
example 60%).
[0046] The subject of the present invention is therefore a composition including a quantity
of polymer blend according to the invention such that the tetrafluoroethylene polymerizate
content, per 100 parts by weight of polymer matrix, is between 0.05 and 10 parts by
weight, preferably 0.05 parts to 6 parts by weight.
[0047] Preferably, the composition further comprises a fire retardant.
[0048] Among the polymers that can be used for the polymer matrix of the compositions according
to the invention, mention may be made of polycarbonate, polyphenylene oxide (PPO),
poly(alkylene terephthalates) such as poly(butylene terephthalate) and poly(ethylene
terephthalate), vinyl polymers such as poly(vinyl chloride), poly(vinyl acetate),
poly(vinyl alcohol), polyalkylenes such as polypropylene and polyethylene, polyacrylates
and polymethacrylates such as poly(methyl acrylate) and poly(methyl methacrylate),
polystyrenes and, in particular high-impact polystyrenes (HIPS), polysulphones and
polyetherimides, acrylonitrile-butadiene-styrene and styrene-acrylonitrile copolymers
and acrylonitrile-butadiene-styrene/polycarbonate blends, poly(phenylene oxide)/polystyrene
blends, and thermoplastic-polyester/polycarbonate blends such as poly(butylene terephthalate)/polycarbonate
blends.
[0049] Preferably, the compositions according to the invention are fire retarded.
[0050] As fire retardants, it is possible to use any known fire-retardant system for the
compositions. Among fire retardants, mention may be made of organophosphates and halogenated
organic compounds. Preferably, brominated aromatic compounds are used such as, for
example, compounds derived from tetrabromobisphenol A. Preferably, still, synergistic
combinations are used that include halogenated aromatic compounds, in particular brominated
compounds, and antimony compounds, such as antimony oxide for example.
[0051] Among organophosphate fire retardants, mention may be made of, inter alia, phenyl
bisdodecyl phosphate, phenyl bisneopentyl phosphate, polyethylene hydrogen phosphate,
phenyl bis (3,5,5'-trimethylhexyl) phosphate, ethyl diphenyl phosphate, 2-ethylhexyl
di-p-tolyl phosphate, diphenyl hydrogen phosphate, bis(2-ethylhexyl) p-tolyl phosphate,
tritolyl phosphate, bis(2-ethylhexyl) phenyl phosphate, trinonyl phosphate, phenyl
methyl hydrogen phosphate, didodecetyl p-tolyl phosphate, tricresyl phosphate, triphenyl
phosphate, halogenated triphenyl phosphate, dibutyl phenyl phosphate, 2-chloroethyl
diphenyl phosphate, 2-ethylhexyl diphenyl phosphate and diphenyl hydrogen phosphate,
possibly in combination with hexabromobenzene and antimony oxide.
[0052] Among halogenated organic compounds which can be used as fire retardants in the compositions
of the present invention, mention may be made of tetrabromobisphenol A, bis(tribromophenoxy)ethane,
poly(bromodiphenyl ether), poly(bromophenol), poly(bromophenyl alkyl ether), poly(bromobenzyl
acrylate) or polyacrylate, poly(bromocyclododecane), poly(bromostyrene), poly(bromophenylmaleimide),
brominated epoxy monomers or epoxy polymers, copolycarbonates derived from a halo-substituted
diphenol and a diphenol, the halogen being preferably chlorine or bromine. Preferably,
this copolycarbonate is the product of a halogenated bisphenol A, such as tetrabromobisphenol
A and tetrachlorobisphenol A, and of a diphenol such as bisphenol A. Preferably, too,
the fire-retarding halogenated organic compound is used in combination with an antimony
compound such as, for example, antimony oxide.
[0053] It is possible to add to the compositions, according to the invention, any conventional
additive such as extenders, reinforcing fillers, pigments, colorants, UV stabilizers,
antioxidants, and impact modifiers.
Examples 4 to 7 and Comparative examples A, B and C
[0054] The mixtures of acrylonitrile-butadiene-styrene and of PTFE/SAN blends according
to the invention, indicated in Table 5 below, were prepared. The quantities of PTFE/SAN
blend added are such that the active polytetrafluoroethylene content is 0.1 parts
by weight per 100 parts of ABS resin.
[0055] The mechanical and fire-resistance properties of the compositions are collated in
Table 6.
[0056] The Vicat test was carried out according to the ISO 306 standard, the Izod impact-strength
test according to the ISO 180 1A standard, the elongation and tensile yield stress
tests according to the ISO 527 standard and the multiaxial impact-strength test according
to the ISO 6603-2 standard.
TABLE 5
|
Comparative example A |
Comparative example B |
Example 4 |
Example 5 |
Comparative Example C |
Example 6 |
Example 7 |
ABS |
100 |
100 |
100 |
100 |
100 |
100 |
100 |
|
bis(tribromophenoxy)ethane [fire retardant] |
23 |
23 |
23 |
23 |
23 |
23 |
23 |
|
Sb2O3 |
4 |
4 |
4 |
4 |
4 |
4 |
4 |
|
Chlorinated polyethylene (CPE) powder |
3 |
|
|
|
|
|
|
|
PTFE powder, 500 µm |
|
0.1 |
|
|
|
|
|
|
Encapsulated 50/50 PTFE/SAN |
|
|
0.2 |
|
|
|
|
|
Encapsulated 60/40 PTFE/SAN |
|
|
|
0.1666 |
|
|
|
|
Coprecipitated 20/80 PTFE/SAN |
|
|
|
|
0.5 |
|
|
|
Encapsulated 40/60 PTFE/SAN |
|
|
|
|
|
0.25 |
|
|
Encapsulated 30/70 PTFE/SAN |
|
|
|
|
|
|
0.333 |
TABLE 6
|
Comparative example A |
Comparative example B |
Example 4 |
Example 5 |
Comparative example C |
Example 6 |
Example 7 |
Vicat B/120 (°C) |
88.9 |
88.6 |
88.8 |
89.3 |
88.9 |
88.8 |
88.9 |
|
Notched Izod impactstrength (kJ/m2) |
12.3 |
10.2 |
9.6 |
9.8 |
10.2 |
10.5 |
10.5 |
|
Total -energy multiaxial impactstrength (Nm) |
18 |
17 |
22 |
23 |
20 |
23 |
24 |
|
Elongation to break normal (%) |
51.87 |
56.75 |
55.55 |
53.25 |
55.85 |
57.93 |
64.98 |
|
Tensile yield stress, normal (MPa) |
42.47 |
43.61 |
43.61 |
43.23 |
43.37 |
42.69 |
42.73 |
|
Elongation to break, weld line (%) |
2.45 |
2.386 |
2.46 |
2.44 |
2.59 |
2.55 |
2.6 |
|
Tensile yield stress, weld line (MPa) |
41.14 |
42.05 |
42.57 |
41.58 |
41.83 |
41.9 |
41.81 |
|
Surface appearance |
good |
fibrous |
good |
good |
good |
good |
good |
|
UL 94, 1.6 mm: |
|
|
|
|
|
|
|
Dripping (flaming droplets) |
yes |
no |
no |
no |
no |
no |
no |
|
Classification |
fails the test |
V-0 |
V-0 |
V-0 |
V-0 |
V-0 |
V-0 |
Comparative examples D to F and Examples 8 to 11
[0057] In the examples below, the proportions of the constituents of the compositions are
expressed in weight per cent with respect to the total weight of the composition.
[0058] As in the previous examples, the compositions indicated in Table 7 below were prepared.
TABLE 7
Examples |
Component |
D |
E |
F |
8 |
9 |
10 |
11 |
PC of 23,000 weight-average molecular weight |
98.92 |
- |
- |
98.992 |
98.956 |
- |
- |
|
PC of 27,000weight-average molecular weight |
- |
98.92 |
98.85 |
- |
- |
98.956 |
98.93 |
|
Mould-release agent |
0.40 |
0.40 |
0.40 |
0.40 |
0.40 |
0.40 |
0.40 |
Fire-retardancy synergist |
0.45 |
0.45 |
0.50 |
0.45 |
0.45 |
0.45 |
0.50 |
|
Antioxidant |
0.05 |
0.05 |
0.05 |
0.05 |
0.05 |
0.05 |
0.05 |
|
80/20 PC (M = 23,000)PTFE dispersion |
0.18 |
0.18 |
0.20 |
- |
- |
- |
- |
|
Encapsulated 50/50 PTFE/SAN |
- |
- |
- |
0.108 |
0.144 |
0.144 |
0.12 |
[0059] The mechanical and fire-resistance properties of the compositions are given in Table
8.
TABLE 8
|
D |
E |
F |
8 |
9 |
10 |
11 |
Notched Izod impact strength (kJ/m2) |
|
|
|
|
|
|
|
at 0°C |
- |
- |
23.0 |
- |
- |
- |
29.1 |
10°C |
|
26.2 |
- |
- |
- |
38.8 |
- |
23°C |
16.4 |
58.5 |
60.3 |
15.3 |
15.1 |
48.5 |
69.0 |
Tensile modulus (MPa) |
2440 |
2402 |
2345 |
2440 |
2394 |
2350 |
2266 |
|
Yield stress (MPa) |
66.5 |
63.0 |
63.5 |
64.6 |
64.3 |
63.4 |
64.2 |
|
Elongation to break (%) |
97.3 |
100.3 |
101.0 |
107.9 |
113.7 |
114.3 |
126.4 |
|
Fire tests |
|
|
|
|
|
|
|
UL 94 - 1.6 mm Classification |
V2 |
V2 |
V1 |
V0 |
V0 |
V0 |
V0 |
|
UL 94 - 2.0 mm Classification |
V0 |
V0 |
- |
V0 |
V0 |
V0 |
- |
[0060] Table B shows that, by using the blend according to the invention in polycarbonate
resins, excellent fire resistance and the best compatibility, as shown by the exceptionally
high values of elongation to break, are obtained.
Comparative examples G to I and Examples 12 to 14
[0061] In the examples below, the proportions of the constituents are given in parts by
weight per 100 parts of resin.
[0062] The mixtures indicated in Table 9 were prepared by mixing pure PTFE and blends according
to the invention with a self-extinguishing PC/ABS polymer blend. The self-extinguishing
PC/ABS blend contains 80 parts by weight of polycarbonate and 20 parts by weight of
acrylonitrile-butadiene-styrene resin, and conventional additives (fire retardants,
antioxidants, lubricants).
TABLE 9
Component |
G |
H |
I |
12 |
13 |
14 |
80/20 PC/ABS |
100 |
100 |
100 |
100 |
100 |
100 |
|
80/20 PC/PTFE dispersion |
1 |
- |
- |
- |
- |
- |
|
Coprecipitated 20/80 PTFE/SAN |
- |
1 |
- |
- |
- |
- |
|
pure PTFE (500 µm) |
- |
- |
0.2 |
- |
- |
- |
|
encapsulated 50/50 PTFE/SAN |
- |
- |
- |
0.4 |
- |
- |
|
encapsulated 40/60 PTFE/SAN |
- |
- |
- |
- |
0.50 |
- |
|
encapsulated 30/70 PTFE/SAN |
- |
- |
- |
- |
- |
0.67 |
[0063] The results of the mechanical and fire-resistance tests of the compositions of Table
9 are given in Table 10.
TABLE 10
Examples |
|
G |
H |
I |
12 |
13 |
14 |
Viscosity in the molten state (Pa.s) |
204 |
197 |
202 |
204 |
201 |
201 |
|
Notched Izod impact strength (kJ/m2) |
36.1 |
44.2 |
29.7 |
45.1 |
43.1 |
44.5 |
|
Multiaxial impact strength |
|
|
|
|
|
|
at room temperature (Nm) |
108 |
131 |
119 |
135 |
137 |
140 |
at -20°C (Nm) |
94 |
109 |
96 |
113 |
110 |
111 |
|
Elongation to break (%) |
30 |
64 |
40 |
73 |
73 |
70 |
|
UL 94: 1.6 mm |
V0 |
V0 |
V0 |
V0 |
V0 |
V0 |
|
UL 94 5 V: 2.5 mm |
fail |
5V |
fail |
5V |
5V |
fail |
[0064] Table 10 shows that the compositions of PC/ABS polymer blends according to the invention
have better multiaxial and Izod impact strengths and exceptional elongation to break,
while still containing good fire-resistance properties.
1. A polymer blend in the form of a free-flowing powder, comprising particles, said particles
comprising a tetrafluoroethylene polymer at least partially encapsulated by a polymer
or copolymer selected from the group consisting of polystyrene, poly-alpha-alkylstyrenes,
styrene-acrylonitrile copolymers, alpha-alkylstyrene-acrylonitrile copolymers, acrylonitrile-butadiene-styrene
copolymers, styrene-butadiene rubbers and their mixtures, and being obtainable by
emulsion polymerization of one or more monomers forming the encapsulating (co)polymer
in the presence of a tetrafluoroethylene polymer latex, said polymer blend being substantially
free of tetrafluoroethylene polymerizate filaments forming a network connecting the
particles of the blend.
2. A polymer blend according to claim 1, characterized in that the encapsulation polymer
or copolymer is obtained by polymerization of monomers or mixtures of monomers which
can be emulsion-polymerized by radical route.
3. A polymer blend according to claim 1 or claim 2, characterized in that the encapulsation
polymer or copolymer is chosen from the group consisting of polystyrene, poly-α-methylstyrene,,
styrene-acrylonitrile copolymers, α-methylstyrene-acrylonitrile copolymers, acrylonitrile-butadiene-styrene
copolymers and their mixtures.
4. A polymer blend according to any one of the preceding claims, characterized in that
the tetrafluoroethylene polymerizate represents 0.01 to 80% by weight with respect
to the total weight of the polymers in the blend.
5. An article obtainable by extrusion moulding, extrusion blow moulding or injection
mouding of a polymer blend according to any one of claims 1 to 4.
6. A process for manufacturing a polymer blend in the form of a free-flowing powder according
to claim 1, comprising emulsion-polymerizing the monomer or the mixture of monomers
forming the encapsulating (co)polymer in the presence of a tetrafluoroethylene polymerizate
latex and recovering the blend in the form of a free-flowing powder.
7. Process according to claim 6, characterized in that the emulsion-polymerizable monomers
are monomers which can be polymerized by radical route and in that the emulsion polymerization
is carried out by radical route.
8. A composition comprising a polymer matrix in which a polymer blend according to any
one of claims 1 to 4 is dispersed, wherein the tetrafluoroethylene polymer content
in the composition is from 0.05 to 10% by weight with respect to the weight of the
polymer matrix.
1. Polymermischung in Form eines frei fließenden Pulvers, umfassend Teilchen, die ein
Tetrafluorethylen-Polymer umfassen, das mindestens teilweise von einem Polymer oder
Copolymer eingekapselt ist, ausgewählt aus der Gruppe bestehend aus Polystyrol, Poly-α-alkylstyrolen,
Styrol-Acrylnitril-Copolymeren, α-Alkystyrol-Acrylnitril-Copolymeren, Acrylnitril-Butadien-Styrol-Copolymeren,
Styrol-Butadien-Kautschuken und deren Mischungen, und die erhältlich sind durch Emulsions-Polymerisation
von ein oder mehreren Monomeren, die das einkapselnde (Co)Polymer bilden, in Gegenwart
einer Tetrafluorethylen-Polymerlatex, wobei die Polymermischung im Wesentlichen frei
ist von Filaments aus Tetrafluorethylen-Polymerisat, die ein Netzwerk bilden, die
die Teilchen der Mischung verbinden.
2. Polymermischung nach Anspruch 1, dadurch gekennzeichnet, dass das einkapselnde Polymer
oder Copolymer erhalten ist durch Polymerisation von Monomeren oder Mischungen von
Monomeren, die radikalisch emulsions-polymerisiert werden können.
3. Polymermischung nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass das einkapselnde
Polymer oder Copolymer ausgewählt ist aus der Gruppe bestehend aus Polystyrol, Poly-α-methylstyrol,
Styrol-Acrylnitril-Copolymeren, α-Methylstyrol-Acrylnitril-Copolymeren, Acrylnitril-Butadien-Styrol-Copolymeren
und deren Mischungen.
4. Polymermischung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass
das Tetrafluorethylen-Polymerisat 0,01 bis 80 Gew.-% mit Bezug auf das Gesamtgewicht
der Polymeren in der Mischung repräsentiert.
5. Gegenstand, erhältlich durch Extrusionsformen, Extrusions-Blasformen oder Spritzgussformen
einer Polymermischung nach einem der Ansprüche 1 bis 4.
6. Verfahren zum Herstellen einer Polymermischung in Form eines frei fließenden Pulvers
gemäß Anspruch 1, umfassend das Emulsions-Polymerisieren des Monomers oder der Mischung
von Monomeren, die das einkapselnde (Co)Polymer bilden, in Gegenwart einer Tetrafluorethylen-Polymerisatlatex
und Gewinnen der Mischung in Form eines frei fließenden Pulvers.
7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, dass die emulsions-polymerisierbaren
Polymeren Monomere sind, die radikalisch polymerisiert werden können, und dass die
Emulsions-Polymerisation radikalisch ausgeführt wird.
8. Zusammensetzung, umfassend eine Polymer-Matrix, in der eine Polymermischung gemäß
einem der Ansprüche 1 bis 4 dispergiert ist, worin der Tetrafluorethylen-Polymergehalt
in der Zusammensetzung von 0,05 bis 10 Gew.-% mit Bezug auf das Gewicht der Polymer-Matrix
ausmacht.
1. Alliage polymère sous forme de poudre s'écoulant librement et comprenant des particules,
ces particules comprenant un polymérisat de tétrafluoroéthylène encapsulées au moins
partiellement par un polymère ou copolymère qui est choisi dans l'ensemble constitué
par le polystyrène, les poly-α-alkylstyrènes, les copolymères styréne/acrylonitrile
(SAN), les copolymères α-alkylstyrène/acrylonitrile, les copolymères acrylonitrile/butadiène/styrène
(ABS), les caoutchoucs styrène/butadiène (SBR), et leurs mélanges, et qui peut être
obtenu par polymérisation en émulsion d'un ou de plusieurs monomères formant le (co)polymère
d'encapsulation, en présence d'un latex de polymérisat de tétrafluoroéthylène, ledit
alliage polymère étant pratiquement exempt de filaments de polymérisat de tétralluoroéthylène
formant un réseau reliant les particules de l'alliage.
2. Alliage polymère selon la revendication 1, caractérisé par le fait que le polymère
ou copolymère d'encapsulation est obtenu par polymérisation de monomères ou de mélanges
de monomères polymérisables en émulsion par voie radicalaire.
3. Alliage polymère selon la revendication 1 ou 2, caractérisé par le fait que le polymère
ou copolymère d'encapsulation est choisi dans l'ensemble constitué par le polystyrène,
le poly-α-méthylstyrène, les copolymères styrène/acrylonitrile (SAN), les copolymères
oc-méthylstyrène/acrylonitrile, les copolymères acrylonitrile/butadiène/styrène (ABS),
et leurs mélanges.
4. Alliage polymère selon l'une quelconque des revendications précédentes, caractérisé
par le fait que le polymérisat de tétrafluoroéthylène représente de 0,01 à 80 % en
poids par rapport au poids total des polymères de l'alliage.
5. Article qui peut être obtenu par extrusion-moulage, extrusion-soufflage ou moulage
par injection d'un alliage polymère selon l'une quelconque des revendications 1 à
4.
6. Procédé de fabrication d'un alliage polymère sous forme d'une poudre s'écoulant librement,
selon la revendication 1, comprenant le fait de polymériser en émulsion le monomère
ou le mélange de monomères formant le (co)polymère d'encapsulation, en présence d'un
latex de polymérisat de tétrafluoroéthylène, et le fait de récupérer l'alliage sous
forme d'une poudre s'écoulant librement.
7. Procédé selon la revendication 6, caractérisé par le fait que les monomères polymérisables
en émulsion sont des monomères polymérisables par voie radicalaire et en ce que la
polymérisation en émulsion s'effectue par voie radicalaire.
8. Composition comprenant une matrice polymère dans laquelle est dispersé un alliage
polymère selon l'une quelconque des revendications 1 à 4, la teneur de la composition
en polymérisat de tétrafluoroéthylène représentant de 0,05 à 10 % en poids par rapport
au poids de la matrice polymère.